WO2024076529A1 - Extrusion de pha à haute humidité - Google Patents

Extrusion de pha à haute humidité Download PDF

Info

Publication number
WO2024076529A1
WO2024076529A1 PCT/US2023/034273 US2023034273W WO2024076529A1 WO 2024076529 A1 WO2024076529 A1 WO 2024076529A1 US 2023034273 W US2023034273 W US 2023034273W WO 2024076529 A1 WO2024076529 A1 WO 2024076529A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyhydroxyalkanoate
resin additive
average molecular
poly
percent
Prior art date
Application number
PCT/US2023/034273
Other languages
English (en)
Inventor
Brock MERCHANT
Ryan Mullins
Original Assignee
Danimer Ipco, Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Danimer Ipco, Llc filed Critical Danimer Ipco, Llc
Publication of WO2024076529A1 publication Critical patent/WO2024076529A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/203—Solid polymers with solid and/or liquid additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B29B7/726—Measuring properties of mixture, e.g. temperature or density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B29B7/92—Wood chips or wood fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0059—Degradable
    • B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0088—Molecular weight
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

Definitions

  • This disclosure relates to biodegradable polymeric compositions. More particularly, this disclosure relates to extrusions of biodegradable polymers, such as polyhydroxyalkanoates, which are extruded under elevated moisture conditions.
  • the method of the present disclosure includes a step of mixing at least one polyhydroxy alkanoate in powder form with at least one resin additive at a temperature from about 120 to about 190 °C to form an extrusion mixture. This mixture is then extruded through an extrusion die to form a resin extrudate comprising the at least one polyhydroxyalkanoate and the at least one resin additive.
  • the at least one polyhydroxyalkanoate in powder form has an initial (i.e., prior to mixing) moisture content of at least 0.10 weight percent, as determined in accordance with ASTM D7191-05, when mixed with the at least one resin additive.
  • the polyhydroxyalkanoate powder may have an even higher moisture content.
  • the least one polyhydroxyalkanoate in powder form may have an initial moisture content of at least 1 weight percent, at least 5 weight percent, at least 10 weight percent, at least 15 weight percent, or even greater, as determined in accordance with ASTM D7191-05, when mixed with the at least one resin additive.
  • the mixing step and the extruding steps are preferably carried out in different devices or in different chambers of the same device.
  • the mixing step is preferably carried out in a low-shear continuous mixer.
  • it is also preferred that the extruding step is carried out in a screw extruder.
  • the at least one polyhydroxyalkanoate preferably has an initial weight average molecular weight before the mixing step and a final weight average molecular weight after the extruding step, which is at least 40 percent of the initial weight average molecular weight, wherein all weight average molecular weights are determined in accordance with ASTM D5296-05. More preferably, the final weight average molecular weight of the at least one polyhydroxyalkanoate is at least 70 percent of the initial weight average molecular weight, still more preferably at least 80 percent of the initial weight average molecular weight, and even more preferably at least 85 percent of the initial weight average molecular weight.
  • polyhydroxyalkanoate A variety of different forms of polyhydroxyalkanoate may be used in the method of the present disclosure.
  • the at least one polyhydroxyalkanoate is made up of poly-3 -hydroxybutyrate-co-3 -hydroxy hexanoate (“P(3HB-co-3HHx)”).
  • P(3HB-co-3HHx) poly-3 -hydroxybutyrate-co-3 -hydroxy hexanoate
  • this P(3HB-co-3HHx) is preferably made up of from about 75 to about 99 mole percent hydroxybutyrate and from about 1 to about 25 mole percent hydroxyhexanoate.
  • the at least one polyhydroxyalkanoate is preferably made up of from about 1 to about 25 weight percent of at least one polyhydroxyalkanoate comprising from about 25 to about 50 mole percent of hydroxy valerate, hydroxyhexanoate, hydroxyoctanoate, and/or hydroxydecanoate.
  • the at least one polyhydroxyalkanoate preferably includes a terpolymer made up from about 75 to about 99.9 mole percent monomer residues of 3 -hydroxybutyrate, from about 0.1 to about 25 mole percent monomer residues of 3-hydroxyhexanoate, and from about 0.1 to about 25 mole percent monomer residues of a third 3 -hydroxyalkanoate having from 5 to 12 carbon atoms.
  • the at least one poly(hydroxyalkanoate) preferably has an initial weight average molecular weight from about 50,000 Daltons to about 2.5 million Daltons, as determined by ASTM D5296-05.
  • the at least one resin additive preferably includes at least one rheology modifier selected from the group consisting of vinyl acetate homopolymers or copolymers, peroxides, epoxides, isocyanates, carbodiimides, and mixtures thereof.
  • the at least one resin additive preferably includes at least one nucleating agent from the group consisting of pentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clays, dipentaerythritol, sorbitol, and mixtures thereof.
  • the at least one resin additive preferably includes at least one filler selected from the group consisting of aragonite, clays, calcium carbonate, cellulose, nano-cellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starches, diatomaceous earth, titanium dioxide, nano clay, mica, and mixtures thereof.
  • the mixing step may also include mixing the at least one polyhydroxyalkanoate in powder form with at least one biopolymer selected from the group consisting of biodegradable polymer selected from the group consisting of polybutylene succinate, polycaprolactone, polybutylene succinate-co-butylene adipate, polybutylene adipate-co-terephthalate, polylactic acid, cellulose acetate, and mixtures thereof.
  • biopolymer selected from the group consisting of biodegradable polymer selected from the group consisting of polybutylene succinate, polycaprolactone, polybutylene succinate-co-butylene adipate, polybutylene adipate-co-terephthalate, polylactic acid, cellulose acetate, and mixtures thereof.
  • the present disclosure provides a method for extruding high-moisture polyhydroxyalkanoates.
  • polyhydroxyalkanoates must be dried to a very low moisture content prior to extrusion to prevent hydrolysis degradation of the polyhydroxy alkanoates.
  • the method of the present disclosure includes a first step of mixing at least one polyhydroxyalkanoate in powder form with at least one resin additive at a temperature from about 120 to about 190 °C to form an extrusion mixture. This mixture is then extruded through an extrusion die to form a resin extrudate comprising the at least one polyhydroxyalkanoate and the at least one resin additive.
  • the at least one polyhydroxyalkanoate in powder form has an unusually high initial moisture content prior to the mixing steps.
  • the least one polyhydroxyalkanoate has an initial (prior to mixing) moisture content of at least 0.1 weight percent, as determined in accordance with ASTM D7191-05, when mixed with the at least one resin additive.
  • the polyhydroxyalkanoate powder may have an even higher moisture content.
  • the least one polyhydroxyalkanoate in powder form may have an initial moisture content of at least 1 weight percent, at least 5 weight percent, at least 10 weight percent, or even at least 15 weight percent, as determined in accordance with ASTM D7191-05, when mixed with the at least one resin additive.
  • the method of the present disclosure may be carried out using a wide variety of forms of polyhydroxyalkanoate, including homopolymers, copolymers, terpolymers, and blends of the foregoing.
  • the polyhydroxyalkanoate may include a homopolymer such as poly(hydroxybutyrate).
  • the polyhydroxyalkanoate may include a copolymer or a terpolymer.
  • the at least one polyhydroxyalkanoate comprises poly-3 -hydroxybutyrate-co-3-hydroxyhexanoate (“P(3HB-co-3HHx)”).
  • this P(3HB-co-3HHx) is preferably made up of from about 75 to about 99 mole percent hydroxybutyrate and from about 1 to about 25 mole percent hydroxyhexanoate.
  • the at least one polyhydroxyalkanoate preferably comprises from about 1 to about 25 weight percent of at least one polyhydroxyalkanoate comprising from about 25 to about 50 mole percent of hydroxy valerate, hydroxyhexanoate, hydroxyoctanoate, and/or hydroxydecanoate.
  • the at least one polyhydroxyalkanoate preferably comprises a terpolymer made up from about 75 to about 99.9 mole percent monomer residues of 3 -hydroxybutyrate, from about 0.1 to about 25 mole percent monomer residues of 3-hydroxyhexanoate, and from about 0.1 to about 25 mole percent monomer residues of a third 3-hydroxyalkanoate having from 5 to 12 carbon atoms.
  • At least one resin additive is mixed with the polyhydroxyalkanoate to form the extrusion mixture.
  • resin additives that may be mixed with the polyhydroxyalkanoates include rheology modifiers, nucleating agents, organic fillers, inorganic fillers, polyesters, and impact modifiers.
  • the at least one resin additive preferably comprises at least one rheology modifier selected from the group consisting of vinyl acetate homopolymers or copolymers, peroxides, epoxides, isocyanates, carbodiimides, and mixtures thereof.
  • the at least one resin additive preferably comprises at least one nucleating agent from the group consisting of pentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clays, dipentaerythritol, sorbitol, and mixtures thereof.
  • the at least one resin additive preferably comprises at least one filler selected from the group consisting of aragonite, clays, calcium carbonate, cellulose, nano-cellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starches, diatomaceous earth, titanium dioxide, nano clay, mica, and mixtures thereof.
  • the mixing step may also include mixing the at least one polyhydroxyalkanoate in powder form with at least one biopolymer selected from the group consisting of biodegradable polymer selected from the group consisting of polybutylene succinate, polycaprolactone, polybutylene succinate-co-butylene adipate, polybutylene adipate-co-terephthalate, polylactic acid, cellulose acetate, and mixtures thereof.
  • the additional biopolymer may be added to the mixture in a weight ratio of from about 1 to about 75 parts by weight of the biopolymer per 100 parts by weight of the at least one polyhydroxyalkanoate.
  • the mixing step and the extruding step are carried out separately. In some instances, the mixing step and the extruding step are carried out in separate devices. In other instances, the mixing step and the extruding step are carried out in separate chambers of a single device.
  • the mixing step is preferably carried out in a continuous mixer, typically operating under relatively low-shear mixing conditions.
  • a suitable mixing system is the Farrel Continuous Mixer, available from Farrel Pomini.
  • a continuous mixer such as the aforementioned Farrel mixer has a mixing chamber with two counter-rotating, non-intermeshing rotors (i.e., screws) for mixing of materials.
  • the flights of the two rotors do not intermesh, and the rotors are sized to provide a relatively large free volume within the mixing chamber.
  • This large free volume within the mixing chamber is due to the lack of intermeshing of the rotor flights and also to the relatively large gap between the screw flights and the wall of the extrusion chamber. In conventional screw extruders, this gap is quite small, and extreme shear is exerted upon the material as it moves through this tight gap.
  • the continuous mixer also allows for internal water cooling to be applied to the extruder screws.
  • the extruder screws are cooled to maintain the material in the mixer at a temperature from about 120 °C to about 190 °C.
  • the extrusion mixer may then be transferred to a conventional screw extruder for the final extruding step.
  • polyhydroxyalkanoates that have been mixed and extruded in accordance with the present disclosure do not exhibit a large degree of polymer degradation due to hydrolysis despite the elevated moisture content of the starring polyhydroxyalkanoates.
  • the at least one poly(hydroxyalkanoate) preferably has an initial (i.e., before mixing with the resin additive) weight average molecular weight from about 50,000 Daltons to about 2.5 million Daltons, as determined by ASTM D5296- 05. More preferably, the at least one poly(hydroxyalkanoate) preferably has an initial weight average molecular weight from about 300,000 Daltons to about 2.5 million Daltons, as determined by ASTM D5296-05
  • the at least one polyhydroxy alkanoate preferably has an initial weight average molecular weight before the mixing step and a final weight average molecular weight after the extruding step, which is at least 40 percent of the initial weight average molecular weight, wherein all weight average molecular weights are determined in accordance with ASTM D5296-05. More preferably, the final weight average molecular weight of the at least one polyhydroxyalkanoate is at least 70 percent of the initial weight average molecular weight, still more preferably at least 80 percent of the initial weight average molecular weight, and even more preferably at least 85 percent of the initial weight average molecular weight.
  • PHA polyhydroxyalkanoate
  • the PHA was a poly-3 -hydroxybutyrate-co-3 -hydroxy hexanoate copolymer, comprising about 6 mole percent 3 -hydroxyhexanoate monomer repeat units.
  • the initial weight average molecular weight of the PHA copolymer was about 1,032,000, as determined by ASTM D5296.
  • the PHA was initially provided as a substantially dry powder.
  • the powder was mixed in a bucket with a known amount of water and stirred with a paint stirrer to provide a PHA sample having a known initial moisture content.
  • Each sample of the PHA was then mixed using a Farrel C-PEX lab scale continuous mixer.
  • the PHA material was fed through the continuous mixer at a rate of about 12 kilograms/hour.
  • the PHA was mixed in the continuous mixer by itself, without any additives.
  • the temperature profile within the continuous mixer was set to 140 °C. Also, the mixing screws within the continuous mixer were internally cooled using chill water.
  • the material After feeding through the continuous mixer, the material is dropped into a conveying screw, which pumps the material to an extrusion die steadily to allow for extrusion and pelletizing.
  • the conveying screw is a single screw extruder set at a temperature range of 120-140 °C.
  • the PHA retained at least 80 % of its initial weight average molecular weight in nearly all cases. In many instances, the PHA retained at least 85 % of its initial weight average molecular weight. Also, the final melt flow index of the PHA was less than 6.0 in nearly all cases and in many cases, less than 5.0 g/10 min. Since the melt flow index generally increases with decreasing molecular weight, these values for the melt flow index also indicate that degradation of the PHA and reduction in weight average molecular weight was relatively small.
  • PHA samples were also prepared.
  • the PHA was a poly-3 -hydroxybutyrate-co-3 - hydroxyhexanoate copolymer, comprising about 6 mole percent 3-hydroxyhexanoate monomer repeat units.
  • the initial weight average molecular weight of the PHA copolymer varied from about 600,000 to about 1,100,00 g/mol, as noted in the table below.
  • the PHA was initially provided as a substantially dry powder.
  • the powder was mixed in a bucket with a known amount of water and stirred with a paint stirrer to provide a PHA sample having a known initial moisture content.
  • control samples were prepared using an Entek 27 mm twin screw lab-scale extruder for comparison purposes.
  • the PHA was heated to a temperature of about 120 - 140 °C and then extruded through a two-hole die into a water bath set at 150 °F to 160 °F (65 °C to 71 °C). The extruded PHA was then cut into pellets.
  • pellets of each PHA sample were tested to determine the final weight average molecular weight of the PHA and the final melt flow index of the PHA.
  • Molecular weight was determined by gel permeation chromatography according to ASTM D5296. Melt flow index was determined according to ASTM D1238 at 175 °C with a 10 kg load. The results are reported in Table 2 below.
  • the observed melt flow index for the comparative examples was also substantially higher than for the preceding examples, which used the continuous mixer.
  • Embodiment 1 A method for extruding a resin which includes polyhydroxyalkanoates, the method comprising the steps of:
  • Embodiment 2 The method of Embodiment 1 , wherein the least one polyhydroxyalkanoate in powder form has an initial moisture content of at least 1 weight percent, as determined in accordance with ASTM D7191-05 when mixed with the at least one resin additive.
  • Embodiment 3 The method of Embodiment 1 or 2, wherein the least one polyhydroxyalkanoate in powder form has an initial moisture content of at least 5 weight percent, more preferably at least 10 weight percent, and even more preferably at least 15 weight percent as determined in accordance with ASTM D7191-05 when mixed with the at least one resin additive.
  • Embodiment 4 The method, according to any of the preceding Embodiments, wherein the mixing step and the extruding steps are carried out in different devices or different chambers of the same device.
  • Embodiment 5 The method, according to any of the preceding Embodiments, wherein the mixing step is carried out in a continuous mixer.
  • Embodiment 6 The method, according to any of the preceding Embodiments, wherein the extruding step is carried out in a screw extruder.
  • Embodiment 7 The method, according to any of the preceding Embodiments, wherein the least one polyhydroxyalkanoate has an initial weight average molecular weight before the mixing step and a final weight average molecular weight after the extruding step, which is at least 40 percent, at least 70 percent, at least 80 percent, or at least 85 percent of the initial weight average molecular weight, wherein all weight average molecular weights are determined in accordance with ASTM D5296-05.
  • Embodiment 8 The method, according to any of the preceding Embodiments, wherein the at least one poly(hydroxyalkanoate) comprises poly-3 -hydroxybutyrate-co-3 - hydroxyhexanoate (“P(3HB-co-3HHx)”).
  • Embodiment 9 The method of Embodiment 8, wherein the P(3HB-co-3HHx) comprises from about 75 to about 99 mole percent hydroxybutyrate and from about 1 to about 25 mole percent hydroxyhexanoate.
  • Embodiment 10 The method, according to any of the preceding Embodiments, wherein the at least one poly(hydroxyalkanoate) comprises from about 1 to about 25 weight percent of at least one polyhydroxyalkanoate comprising from about 25 to about 50 mole percent of hydroxyvalerate, hydroxyhexanoate, hydroxyoctanoate, and/or hydroxydecanoate.
  • Embodiment 11 The method, according to any of the preceding Embodiments, wherein the at least one poly(hydroxyalkanoate) comprises a terpolymer made up from about 75 to about 99.9 mole percent monomer residues of 3 -hydroxy butyrate, from about 0.1 to about 25 mole percent monomer residues of 3 -hydroxyhexanoate, and from about 0.1 to about 25 mole percent monomer residues of a third 3 -hydroxy alkanoate having from 5 to 12 carbon atoms.
  • Embodiment 12 The method, according to any of the preceding Embodiments, wherein the at least one poly(hydroxyalkanoate) has an initial weight average molecular weight from about 50,000 Daltons to about 2.5 million Daltons, as determined by ASTM D5296-05.
  • Embodiment 13 The method, according to any of the preceding Embodiments, wherein the at least one resin additive comprises at least one rheology modifier selected from the group consisting of vinyl acetate homopolymers or copolymers, peroxides, epoxides, isocyanates, carbodiimides, and mixtures thereof.
  • the at least one resin additive comprises at least one rheology modifier selected from the group consisting of vinyl acetate homopolymers or copolymers, peroxides, epoxides, isocyanates, carbodiimides, and mixtures thereof.
  • Embodiment 14 The method, according to any of the preceding Embodiments, wherein the at least one resin additive comprises at least one nucleating agent from the group consisting of pentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clays, dipentaerythritol, sorbitol, and mixtures thereof.
  • the at least one resin additive comprises at least one nucleating agent from the group consisting of pentaerythritol, boron nitride, poly(hydroxybutyrate), inositol, clays, dipentaerythritol, sorbitol, and mixtures thereof.
  • Embodiment 15 The method, according to any of the preceding Embodiments, wherein the at least one resin additive comprises at least one filler selected from the group consisting of aragonite, clays, calcium carbonate, cellulose, nano-cellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starches, diatomaceous earth, titanium dioxide, nano clay, mica, and mixtures thereof.
  • the at least one resin additive comprises at least one filler selected from the group consisting of aragonite, clays, calcium carbonate, cellulose, nano-cellulose, talc, kaolinite, montmorillonite, bentonite, silica, chitin, starches, diatomaceous earth, titanium dioxide, nano clay, mica, and mixtures thereof.
  • the mixing step further comprises mixing the at least one polyhydroxyalkanoate in powder form with at least one biopolymer selected from the group consisting of biodegradable polymer selected from the group consisting of polybutylene succinate, polycaprolactone, polybutylene succinate-co-butylene adipate, polybutylene adipate-co- terephthalate, polylactic acid, cellulose acetate, and mixtures thereof.
  • biopolymer selected from the group consisting of biodegradable polymer selected from the group consisting of polybutylene succinate, polycaprolactone, polybutylene succinate-co-butylene adipate, polybutylene adipate-co- terephthalate, polylactic acid, cellulose acetate, and mixtures thereof.

Abstract

La présente invention concerne un procédé d'extrusion de polyhydroxyalcanoates à haute humidité. Le procédé comprend une étape de mélange d'au moins un polyhydroxyalcanoate sous forme de poudre et ayant une teneur en humidité initiale d'au moins 0,10 pour cent en poids, avec au moins un additif de résine à une température d'environ 120 à environ 190 °C pour former un mélange d'extrusion. Ce mélange est ensuite extrudé à travers une filière d'extrusion pour former un extrudat de résine comprenant ledit polyhydroxyalcanoate et ledit additif de résine.
PCT/US2023/034273 2022-10-03 2023-10-02 Extrusion de pha à haute humidité WO2024076529A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202263412670P 2022-10-03 2022-10-03
US63/412,670 2022-10-03

Publications (1)

Publication Number Publication Date
WO2024076529A1 true WO2024076529A1 (fr) 2024-04-11

Family

ID=88695711

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2023/034273 WO2024076529A1 (fr) 2022-10-03 2023-10-02 Extrusion de pha à haute humidité

Country Status (1)

Country Link
WO (1) WO2024076529A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030108701A1 (en) * 2001-10-19 2003-06-12 The Procter & Gamble Company Polyhydroxyalkanoate copolymer/starch compositions for laminates and films
US20040225269A1 (en) * 2003-05-08 2004-11-11 The Procter & Gamble Company Molded or extruded articles comprising polyhydroxyalkanoate copolymer and an environmentally degradable thermoplastic polymer
US20160060451A1 (en) * 2013-04-10 2016-03-03 Bio-Tec Biologische Naturverpackungen Gmbh & Co. Kg Polymer composition
US20170362396A1 (en) * 2015-03-05 2017-12-21 Kaneka Corporation Method of producing polyester resin composition and method of producing polyester resin formed article, and polyester resin composition and polyester resin formed article
CN109181064A (zh) * 2018-08-15 2019-01-11 句容协鑫集成科技有限公司 一种耐高电压接线盒的制备方法
US20200384750A1 (en) * 2018-03-30 2020-12-10 Mitsubishi Chemical Corporation Biodegradable laminate
US20220002504A1 (en) * 2018-11-21 2022-01-06 Biofibre Gmbh Method of manufacturing biocomposite materials comprising cellulose
US11235497B2 (en) * 2014-12-23 2022-02-01 Bio-Tec Biologische Naturverpackungen Gmbh, & Co. Kg Method for producing moulded parts

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030108701A1 (en) * 2001-10-19 2003-06-12 The Procter & Gamble Company Polyhydroxyalkanoate copolymer/starch compositions for laminates and films
US20040225269A1 (en) * 2003-05-08 2004-11-11 The Procter & Gamble Company Molded or extruded articles comprising polyhydroxyalkanoate copolymer and an environmentally degradable thermoplastic polymer
US20160060451A1 (en) * 2013-04-10 2016-03-03 Bio-Tec Biologische Naturverpackungen Gmbh & Co. Kg Polymer composition
US11235497B2 (en) * 2014-12-23 2022-02-01 Bio-Tec Biologische Naturverpackungen Gmbh, & Co. Kg Method for producing moulded parts
US20170362396A1 (en) * 2015-03-05 2017-12-21 Kaneka Corporation Method of producing polyester resin composition and method of producing polyester resin formed article, and polyester resin composition and polyester resin formed article
US20200384750A1 (en) * 2018-03-30 2020-12-10 Mitsubishi Chemical Corporation Biodegradable laminate
CN109181064A (zh) * 2018-08-15 2019-01-11 句容协鑫集成科技有限公司 一种耐高电压接线盒的制备方法
US20220002504A1 (en) * 2018-11-21 2022-01-06 Biofibre Gmbh Method of manufacturing biocomposite materials comprising cellulose

Similar Documents

Publication Publication Date Title
US8841362B2 (en) Thermoplastic starch and synthetic polymer blends and method of making
EP2467418B1 (fr) Procédé de production de mélanges amidon thermoplastique/polymère
KR100479775B1 (ko) 열가소성 가공가능한 전분 또는 전분유도체 폴리머 혼합물
Li et al. Comparative study on the blends of PBS/thermoplastic starch prepared from waxy and normal corn starches
US5051222A (en) Method for making extrudable polyvinyl alcohol compositions
EP1780234A1 (fr) Acide polylactique et son processus de production
US11884807B2 (en) Process and apparatus for manufacture of processable polyvinyl alcohol
WO2005113616A2 (fr) Melange amidon-polyester obtenu par extrusion reactive
CA2072525A1 (fr) Composition de polymeres d'amidon et d'acrylate qu'on peut traiter par thermoplastie
JP2010540750A (ja) 生分解性ポリマーとアクリル系共重合体とのブレンド
EP0415357B1 (fr) Compositions d'alcool polyvinyliques extrudables
US11203648B2 (en) Esterified starch and starch-containing plastic composition
JP2022519531A (ja) 澱粉混合物の調製方法
WO2024076529A1 (fr) Extrusion de pha à haute humidité
CN113512281B (zh) 一种改性pga材料及其制备方法，以及改性pga薄膜
CN111087766A (zh) 热塑性共混物材料及共混物热塑性薄膜及其制备方法
CN107793592B (zh) 生物降解脂肪族芳香族共聚酯增韧热塑性聚多糖共混物及其制备方法和薄膜
KR101139654B1 (ko) 생분해성 고분자 간의 블렌드 상용화 방법
CN107936443B (zh) 热塑性薄膜及制备方法
CN107793589B (zh) 热塑性纤维素与脂肪族共聚酯共混物及制备方法
CN107793591B (zh) 生物降解聚酯增韧热塑性聚多糖共混物及其制备方法和薄膜
CN107936444B (zh) 接枝改性的热塑性纤维素与脂肪族聚酯共混物及制备方法
CN107793713B (zh) 热塑性纤维素与脂肪族共聚酯共混物薄膜及制备方法
KR100257036B1 (ko) 반응성이 우수한 열가소성 전분의 제조방법, 이를 함유하는 수지조성물 및 복합재료
KR20190072296A (ko) 생분해성 고분자 조성물의 제조방법